Subduction zone magmas are more oxidised on eruption than those at mid-ocean ridges. This is attributed either to oxidising components, derived from subducted lithosphere (slab) and added to the mantle wedge, or to oxidation processes occurring during magma ascent via differentiation. Here we provide direct evidence for contributions of oxidising slab agents to melts trapped in the sub-arc mantle. Measurements of sulfur (S) valence state in sub-arc mantle peridotites identify sulfate, both as crystalline anhydrite (CaSO₄) and dissolved SO₄²⁻ in spinel-hosted glass (formerly melt) inclusions. Copper-rich sulfide precipitates in the inclusions and increased Fe³⁺/∑Fe in spinel record a S⁶⁺–Fe²⁺ redox coupling during melt percolation through the sub-arc mantle. Sulfate-rich glass inclusions exhibit high U/Th, Pb/Ce, Sr/Nd and δ³⁴S (+ 7 to + 11‰), indicating the involvement of dehydration products of serpentinised slab rocks in their parental melt sources. These observations provide a link between liberated slab components and oxidised arc magmas.

We report petrographic, major and trace element data for xenoliths from the andesitic Avacha volcano (Kamchatka), which host orthopyroxene (opx)-rich veins of mantle origin formed either by rapid crystallization of intruded melts or by their interaction with the host harzburgite. Studies of such veins may give better insights into sub-arc mantle processes (in particular on a millimetre to centimetre scale) than those of (1) arc xenoliths that do not preserve solidified initial metasomatizing agents, (2) massif peridotites, probably modified during their emplacement, or (3) arc magmatic rocks, which provide indirect information. We seek to trace the evolution of these agents as they react with the host peridotite and to assess their impact on the wall-rocks. The veins cross-cut spinel harzburgite and consist mainly of opx with minor olivine, clinopyroxene (cpx) and/or amphibole. We identify ‘rapidly crystallized’ veins that cut wall-rock olivine without petrographic evidence of reaction, and ‘reactive’ veins subdivided into ‘thick’ (0·5–1 mm) and ‘thin’ (<€0·5 mm). Minerals in the rapidly crystallized veins are depleted in rare earth elements (REE) and high field strength elements (HFSE) and enriched in fluid-mobile elements relative to REE. Minerals in the reactive veins have higher Ti, Al, Cr and alkalis than minerals in the rapidly crystallized veins, as well as highly variable trace element abundances, especially in reaction zones, thin veins and related metasomatic pockets in the host peridotite. They commonly show U-shaped REE patterns and positive Zr and Hf spikes in normalized trace element patterns. Our data, supported by recent reports, show that the rapidly crystallized veins formed between 1200°C and 900°C from a liquid derived by fluid-fluxed melting of a refractory (harzburgitic) mantle source depleted in heavy REE. The reactive veins formed via ‘fractionation–reactive percolation’ from fractionated hydrous derivatives of the melts that precipitated the rapidly crystallized veins. These liquids re-equilibrated with the host through diffusion and fluid-assisted dissolution–precipitation reactions, whose end-products are thin reactive veins and metasomatic pockets with distinctive U-shaped REE patterns and Zr–Hf spikes. Some Avacha xenoliths contain veins of Fe-rich amphibole deposited from the host magma that penetrated fractures in the peridotite fragments during their transport to the surface. These products of contamination were mistakenly attributed to mantle metasomatism in previous studies of other suites of Avacha mantle xenoliths. Trace element abundances in such veins are higher than for reactive veins of mantle origin, but both have similar trace element patterns (U-shaped REE patterns and Zr–Hf spikes) suggesting that ‘fractionation–reactive percolation’ also took place during their formation and is common during interaction of refractory peridotites with percolating melts and fluids. Metasomatic pockets of cpx and amphibole replacing coarse opx and spinel in the host peridotites commonly occur in the vicinity of fractures that lead to reactive opx-rich veins. The cpx and amphiboles in the pockets show progressive depletion in middle REE and HFSE at constant light REE and/or large ion lithophile elements away from the veins towards the host. This indicates that residual hydrous fluids expelled from the source veins enriched the wall-rock peridotites in incompatible elements but were progressively modified by reaction with the host with increasing percolation distance. This process produces disseminated pockets of metasomatic minerals with a broad range of compositions from a single initial liquid and strongly affects the trace element budgets of the harzburgite xenoliths from Avacha. We show that melts and fluids are likely to undergo profound transformation as they travel through and react with the refractory host mantle, even on a millimetre to centimetre scale. The composition of the initial metasomatizing agents can only be inferred from the composition of the metasomatic phases in mantle rocks combined with appropriate partition coefficients if these phases come from well-equilibrated mineral assemblages located close to melt and/or fluid sources.

Island arc picrites and boninites are magnesian magmatic rocks believed to be generated by high degrees of melting of depleted mantle sources fluxed by subduction-derived, volatile-rich components. These magmas can be probes of both the mantle wedge protoliths and subduction components, but are rare among other, usually more evolved, types of arc lavas. Furthermore, many arc picrites and boninites show evidence for late-stage differentiation prior to or during eruption, masking their primary, mantle-derived geochemical signatures. We report textural and chemical data on spinel-hosted melt inclusions of mantle origin in amphibole-bearing websterite veins cross-cutting spinel harzburgite xenoliths from the active andesitic Avacha volcano (south Kamchatka, Russia). The data are used to constrain the composition and origin of melts that formed the websterite veins in the sub-arc lithospheric mantle. The melt inclusions typically contain euhedral orthopyroxene and clinopyroxene and occasionally minor amphibole in silicate glass. The melt inclusions were homogenized using heating stages and gas-mixing furnaces. The homogenized glasses range from subalkaline primitive silica-rich picrite and high-Ca boninite (>15 wt % MgO, 48–54 wt % SiO₂) to rhyolite. High-Ca boninite glasses have moderate volatile and low heavy rare earth element contents and elevated Cs, Rb, Ba, U, Sr, and Li abundances, with extremely high U/Th. In turn, the glasses display no negative spikes in the high field strength elements Nb, Ta, Zr, Hf, and Ti. We show that the silica-rich picrite and high-Ca boninite liquids in this study formed by high degrees of melting (>25%), at volatile under-saturation, of hybrid melt-depleted but silica-rich mantle sources at ≥1·5 GPa. The hybrid sources formed in two stages: first, by extraction of ∼15% melt from the convecting mantle to form a refractory protolith, which was subsequently enriched in silica via interaction with subduction-derived components prior to or during remelting in the mantle wedge. The subduction-derived components were enriched in fluid-mobile elements and probably oxidized. Overall, our results suggest that silica-rich picrites and high-Ca boninites can be primary melts in mature subduction zones and differentiate within the mantle wedge and the deep arc crust to form more evolved andesite magmas.

We report abundances of major trace and volatile elements in an orthopyroxenite vein cutting a sub-arc, mantle-derived, spinel harzburgite xenolith from Kamchatka. The orthopyroxenite contains abundant sulfides and is characterized by the presence of glass (formerly melt) both interstitially and as inclusions in minerals, comparable with similar veins from the West Bismarck arc. The glass formed by quenching of residual melts following crystallization of abundant orthopyroxene, amphibole, and minor olivine and spinel. The interstitial glass has a low-Ti, high-Mg# andesite composition, with a wide range of H₂O and S contents but more limited F and Cl variations. We calculate trace element partition coefficients using mineral and glass data, including those for halogens in amphibole, which agree with experimental results from the literature. Despite having a similar, high-Mg# andesite composition, the orthopyroxene-hosted glass inclusions usually contain much more H₂O and S than the interstitial glass (4–7 wt% and ∼2,600 ppm, respectively). The initial vein-forming melts were oxidized, recording oxygen fugacity conditions up to ∼1.5 log units above the fayalite–magnetite–quartz oxygen buffer. They intruded the sub-arc mantle lithosphere at ≥1,300°C, where they partially crystallized to form high-Mg# andesitic derivative melts at ca. 1,050–1,100°C. Comparison with literature data on glass-free orthopyroxenite veins from Kamchatka and the glass-bearing ones from West Bismarck reveals fundamental similarities indicating common parental melts, which were originally produced by low-degree melting (≤5%) of spinel harzburgite at ≥1,360°C and ≤1.5 GPa. This harzburgite source likely contained ≤0.05 wt% H₂O and a few ppm of halogens. Volatile evolution inferred from glass compositions shows that (i) redox exchange between S⁶⁺ in the original melt and Fe²⁺ in the host mantle minerals, together with (ii) the formation of an S-bearing, (H₂O, Cl)-rich hydrothermal fluid from the original melt, provides the conditions for the formation of abundant sulfides in the orthopyroxenites during cooling. During this process, up to 85% of the original melt S content (∼2,600 ppm) is locally precipitated as magmatic and hydrothermal sulfides. As such, melts derived from spinel harzburgite sources can concentrate chalcophile and highly siderophile metals in orthopyroxenite dykes and sills in the lithosphere.